Photographic processes and recording materials for use therein

ABSTRACT

A process for the formation of transfer images in colour formed by: I. IMAGE-WISE EXPOSURE TO ELECTROMAGNETIC RADIATION OF A PHOTOGRAPHIC MATERIAL, WHICH CONTAINS A SILVER HALIDE EMULSION LAYER HAVING IN EFFECTIVE CONTACT WITH THE SILVER HALIDE GRAINS, WHICH ARE SENSITIVE TO SAID RADIATION, A DEVELOPING AGENT THAT IS RESISTANT TO DIFFUSION IN A HYDROPHILIC COLLOID MEDIUM AND HAVING IN EFFECTIVE CONTACT WITH SAID DEVELOPING AGENT AT LEAST ONE COLOURLESS REAGENT THAT IS CAPABLE: 1. OF DIFFUSING IN AQUEOUS ALKALINE MEDIUM FROM SAID PHOTOGRAPHIC MATERIAL TO A RECEPTOR MATERIAL, 2. OF FORMING A DYESTUFF BY OXIDATIVE INTERMOLECULAR OR INTRAMOLECULAR COUPLING OR COUPLING WITH A DIFFERENT COLOURLESS REAGENT BEING LIKEWISE CAPABLE OF DIFFUSING IN THE AQUEOUS ALKALINE MEDIUM, AND 3. OF FORMING WITH THE OXIDATION PRODUCT OF SAID DEVELOPING AGENT A COMPOUND HAVING A SUBSTANTIALLY SMALLER DIFFUSION MOBILITY THAN IT HAS IN UNREACTED STATE, II. CONTACTING THE EXPOSED PHOTOGRAPHIC MATERIAL WITH AN AQUEOUS ALKALINE ACTIVATING LIQUID TO BRING ABOUT THE REDUCING ACTION OF THE DEVELOPING AGENT THEREBY FORMING IN THE EXPOSED PORTIONS A SILVER IMAGE AND AN OXIDATION PRODUCT OF THE DEVELOPING AGENT THAT COUPLES WITH SAID COLOURLESS REAGENT(S) TO FORM IN THE EXPOSED PORTIONS OF THE EMULSION LAYER (A) COMPOUND(S) THAT POSSESS(ES) A SUBSTANTIALLY LOWER DIFFUSION MOBILITY THAN THE UNREACTED REAGENTS HAVE, AND III. TRANSFERRING FROM THE TREATED PHOTOGRAPHIC MATERIAL AN AMOUNT OF (THE) REAGENT(S) THAT REMAINED CAPABLE OF DIFFUSING BY MEANS OF THE ALKALINE PROCESSING LIQUID ONTO A RECEIVING MATERIAL WHEREON TRANSFERRED REAGENT IS INTERMOLECULARLY OR INTRAMOLECULARY OXIDATIVELY COUPLED, OR SAID DIFFERENT REAGENTS ARE OXIDATIVELY COUPLED BY MEANS OF AN OXIDISING AGENT. Useful diffusion-resistant developing agents are of the paraphenylene diamine type. Useful colourless reagents are selected from the class of Alpha -naphthol, phenol, reactive methylene or N,N-dialkylaniline type coupler compounds capable of oxidatively coupling with a different colourless reagent being a hydrazone compound in order to form dyes containing an azino group. The intramolecularly coupling compounds contain as a first group the reactive part of one of said coupler compounds chemically liked to a second group containing the hydrazone structure.

United States Patent [191 Janssens et al.

Oct. 1, 1974 1 1 PHOTOGRAPHIC PROCESSES AND RECORDING MATERIALS FOR USE THEREIN Inventors: Wilhelmus Janssens, Aarschot;

Raymond Gerard Lemahieu, Mortsel, both of Belgium Agfa-Gevaert N.V., Mortsel, Belgium Filed: Mar. 30, 1972 Appl. No.: 239,598

[73] Assignee:

Foreign Application Priority Data Mar. 31, 1971 Great Britain 8338/71 Oct. 14, 1971 Great Britain 47883/71 US. Cl 96/3, 96/29 D, 96/77 Int. Cl. G03c 7/00, G030 5/54, G03c 1/40 Field of Search 96/3, 77, 29 D References Cited UNITED STATES PATENTS 5/1961 Rogers 96/3 5/1968 Schranz et al. 96/77 12/1971 Puschel et a1 96/3 Primary ExaminerRonald H. Smith Assistant ExaminerRichard L. Schilling Attorney, Agent, or FirmWil1iam J. Daniel [57] ABSTRACT A process for the formation of transfer images in colour formed by:

,para-phenylene diamine type.

1. of diffusing in aqueous alkaline medium from said photographic material to a receptor material,

2. of forming a dyestuff by oxidative intermolecular or intramolecular coupling or coupling with a different colourless reagent being likewise capable of diffusing in the aqueous alkaline medium, and

3. of forming with the oxidation product of said developing agent a compound having a substantially smaller diffusion mobility than it has in unreacted state,

ii. contacting the exposed photographic material with an aqueous alkaline activating liquid to bring about the reducing action of the developing agent thereby forming in the exposed portions a silver image and an oxidation product of the developing agent that couples with said colourless reagent(s) to form in the exposed portions of the emulsion layer (a) compound(s) that possess(es) a substantially lower diffusion mobility than the unreacted reagents have, and

iii. transferring from the treated photographic material an amount of (the) reagent(s) that remained capable of diffusing by means of the alkaline processing liquid onto a receiving material whereon transferred reagent is intermolecularly or intramoleculary oxidatively coupled, or said different reagents are oxidatively coupled by means of an oxidising agent.

Useful diffusion-resistant developing agents are of the Useful colourless reagents are selected from the class of a-naphthol, phenol, reactive methylene or N,N-dialkylaniline type coupler compounds capable of oxidatively coupling with a different colourless reagent being a hydrazone compound in order to form dyes containing an azino group. The intramolecularly coupling compounds contain as a first group the reactive part'of one of said coupler compounds chemically liked to a second group containing the hydrazone structure.

25 Claims, 2 Drawing Figures A A A A A A A A A A A A A(- 'A A A AA A A A A A A A A Aj A A AA -3 4 A A A A A A A RA A A A A A A -5 4-n-u6 PHOTOGRAPHIC PROCESSES AND RECORDING MATERIALS FOR USE THEREIN This invention relates to photographic processes for the production of colour images and to photographic materials for use in such processes.

Several techniques have been proposed for the production of monochromatic as well as multicolour pictures by image-wise diffusion transfer of compounds soluble in one of the photographic processing liquids.

Among these processes the process based on the use of so-called dye developers has become of practical importan'ce.

In such a process described e.g. in the US. Pat. No. 2,983,606 of Howard G. Rogers, issued May 9, 1961, a photographic silver halide material is used containing a reagent, which is a dye possessing a developing function and which, when oxidized, provides areaction product of lower solubility in a processing liquid than the unreacted reagent. Relying on said property of the dye developer a colour diffusion transfer process was realized, which made possible the production of positive monochromatic or multicolour prints stating from a monolayer or multilayer silver halide material containing the proper dye developer compounds.

A multilayer colour photographic material suited for use in said process has silver halide emulsion layers that are spectrally sensitive to blue, green and red light respectively and comprises three alkali-permeable colloid layers each of which is adjacent to a said emulsion layer and contains a different dye developer compound of a colour complementary to that the. adjacent silver halide emulsion layer has been spectrally sensitized to. Such multilayer colour photographic material is not suited for reflex emposure since .each dye developer layer acts as an absorption layer for the reflected light to which the corresponding silver halide emulsion layer is sensitive.

According to the present invention a photographic material, suitable for use in a process for the production of dye images by image-wise diffusion transfer of compounds soluble in an alkaline aqueous processing liquid, contains photosensitive silver halide grains dispersed in a hydrophilic colloid layer and contains in or in water-permeable relation to such layer at least one colourless reagent, which is capable of forming a dyestuff by an oxidative coupling reaction and of diffusing in aqueous alkaline meduim from said material to a re ceptor material, said photographic material also containing in effective contact with said silver halide grains a developing agent, which is resistant to diffusion in a hydrophilic colloid medium and which when activated in the presence of an alkaline aqueous liquid after the image-wise exposure of said layer reduces the exposed silver halide in said layer and which couples in oxidized state with the colourless reagent to inhibit its diffusion from the exposed portions of the photosensitive material into the receptor material.

The process for the formation of transfer colour images according to the present invention comprises the steps of:

a. image-wise exposing to electromagnetic radiation a photographic material, which contains a silver halide emulsion layer having in effective contact with the silver halide grains that are sensitive or have been sensitized to said electromagnetic radiation a developing agent that is resistant to diffusion in a hydrophilic colloid medium and having in effective contact with said developing agent at least one colourless reagent that is capable of diffusing in aqueous alkaline medium from said material to a receptor material and of forming a dyestuff by oxidative intermolecular or intramolecular coupling or coupling with another different colourless rea-- gent being likewise capable of diffusing in aqueous alkaline medium and of forming wiht the oxidation product of said developing agent a compound havpound(s) that posesses(es) a substantially lower diffusion mobility than the unreacted reagents have,

. transferring from the thus treated material an amount of the reagent molecules that remained capable of diffusing by means of the alkaline processing liquid onto a receiving material whereon transferred identical reagent molecules are intermolecularly or intramolecularly oxidatively coupled, or different reagent molecules are oxidatively coupled, the oxidative coupling proceeding with an oxidizing agent, which is stronger than exposed silver halide and resulting in the formation of a dye image on the receiving material.

According to a first embodiment of the invention the photosensitive layer has associated therewith a pair of different colourless reagents (called A and B respectively) for forming a dye by oxidative coupling and a developing agent for developing that layer and forming an oxidation product that inhibits diffusion of at least one of such reagents.

According to a second embodiment of the invention the photosensitive layer has associated therewith a colourless reagent for forming such a dyestuff by oxidative intermolecular or intramolecular coupling, and a developing agent for developing that layer so that an oxidation product forms that inhibits diffusion of said reagent.

For the operation with a photosensitive layer suitable for use in said first embodiment, the process for forming a dye image by image-wise transfer of colourforming reactant comprises the following steps:

a. image-wise exposing a photographic material containing a silver halide emulsion layer having in effective contact with its photosensitive silver halide grains a developing agent that is resistant to diffusion in a hydrophilic colloid medium and in effective contact with said developing agent a pair of colourless reagents that are capable of diffusing in said medium with the aid of an aqueous alkaline liquid and that are capable of forming a dyestuff by oxidative coupling with each other and of which at least one of said reagents being capable of forming with the oxidation product of the said developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,

b. contacting the exposed recording material with an aqueous alkaline activating liquid to bring about the reducing action of the developing agent thereby forming in the exposed portions a silver image and a developer oxidation product that couples with at least one of said colourless reagents to form in the emulsion layer a compound that possesses a substantially lower diffusion mobility than the unreacted reagent,

c. arranging the thus treated recording material in close relationship with a receptor material to transfer thereto the residual unaffected dye-forming reagents by means of the processing liquid, and to bring abqut: oxidative coupling of such reagents in or on said receptor material by means of an oxidizing agent, which is stronger than the exposed silver halide resulting in the formation of a dye image in the receptor material, and

d. separating the photographic material from the receptor material.

By effective contact is meant here that the substances that have to co-operate in the processing of the exposed recording material are provided in the recording material at the right time and in the appropriate location to operate in the desired way in the imageformation.

If there is only one said silver halide emulsion layer with associated developing agent and colour-forming reagentsthe process leads to the formation of a monochromatic image. However, the photographic material may comprise a plurality of light-sensitive layers sensitive in different spectral regions and different associated pairs of colour-formers as above referred to so that plural-colour image of a plural-colour original can be produced on the receptor material.

According to the first embodiment of the present invention a dye image of an individual colour can be formed on a receptor material by means of a photosensitive recording material comprising a sheetlike support and a hydrophilic colloid silver halide emulsion layer containing in effective contact with the silver halide a p-phenylene diamino type developing agent resisting d t usiqntamiamizlure et ye m g QIHEQPEQA and a dye forming compound B, which are both capable of diffusing from their hydrophilic colloid layer by means of an alkaline aqueous liquid.

Compound A as well as compound B are incorporated in the same silver halide emulsion layer or one or both of them can be incorporated in a colloid layer subjacent to the silver halide emulsion layer so that the compound(s) which has or have to be immobilized can be intercepted by the oxidized developing agent resisting diffusion.

Whereas in the production of monochromatic images no measures have to be taken to avoid unwanted coupling between separate colourless dye-forming reaction partners, such is not the case in reproduction materials by means of which multicolour images have to be manufactured. It is known that in order to produce a true multicolour print by a substractive multicolour reproduction system three dye images having the complementary colours yellow, magenta and cyan respectively have to be formed in register.

In a multicolour reproduction material that is suited for the production of multicolour prints according to the present invention the colourless dye-forming reagents are grouped in three pairs, in which the reagents of each different pair form on the receptor material by oxidatively coupling a dye of a different complementary colour, viz. a yellow, magenta and cyan dye respectively.

In practice, in the production of said multicolour pr t e r ac P r of e chm r ofrp t crsl which are not immobilized image-wise by reaction with the developer oxidation product, have to be the same for each pair since otherwise the oxidative coupling between image-wise transferred and overall transferred couplers proceeding along the same reaction mechanism for all the pairs would yield on the receiving material false colours resulting from the oxidative coupling of one partner of a pair with a coupler of another pair.

However, in the case both of the reaction partners of each pair are immobilized during the development it is indifferent which type of reagents is common to all of the pairs.

The photographic material incorporates in the or each light-sensitive layer a diffusion-resistant developing agent, which under the conditions of photographic processing is capable of preferentially reducing exposed silver halide to silver, i.e., of developing a latent image in an exposed silver halide emulsion.

When operating with a photosensitive layer suitable for use in said second embodiment the process for forming a dye image by image-wise transfer of colour forming reactant comprises the following steps:

a. image-wise exposing a photographic material containing a silver halide emulsion layer having in effective contact with its photosensitive silver. halide grains a developing agent that is resistant to diffusion in a hydrophilic colloid medium and in effective contact with said developing agent a colourless reagent that is capable of diffusing in said medium with the aid of an aqueous alkaline liquid, of forming a dyestuff by oxidative intermolecular or intramolecular coupling, and of forming with the oxidation product of said developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,

b. contacting the exposed recording material with an aqueous alkaline activating liquid to bring about the reducing action of the developing agent, thereby forming in the exposed portions a silver image and a developer oxidation product that couples with said colourless reagent to form in the emulsion layer a compound that possesses substantially lower diffusion mobility than the unreacted reagent has,

c. arranging the thus treated recording material in close relationship with a receptor material to transfer thereto the residual unaffected dye-forming reagent be means of the alkaling liquid, and to bring about oxidative coupling of said reagent by means of an oxidising agent, which is stronger than the exposed silver halide resulting in the formation of a dye image in the receptor material, and

d. separating the photographic material from the receptor material.

By intermolecular oxidative coupling is meant that two separate molecules of the colourless dye-forming reagent oxidatively couple with each other to form a dye molecule.

By intramolecular oxidative coupling is meant that two reactive parts of the same molecule of the colourless dye-forming reagent are oxidatively coupled and form a dye molecule. Compounds for one of these types of coupling will be illustrated further on by a particular example.

The colourless colour-forming reagents for intermolecular or intramolecular coupling may be considered as consisting of two chemically linked structural parts C and C forming a compound having the general formula:

wherein:

C in the intermolecular reaction o xidatively couples with the group C of a second molecule C -C and wherein C, in the intramolecular reaction after a rearrangement oxidatively couples with the group C2 of the molecule to which C itself belongs.

Having described in the preceding the principles of the invention and of some preferred embodiments and materials and having given a preliminary explanation of its utility, we now present details on preferred substances used in the present photographic process.

In a preferred embodiment of the present invention a silver halide developing agent known from silver halide colour photography is used being resistant to diffusion and capable of reacting with a phenol type or reactive methylene group type colour coupler. Such developing agent is preferably an aromatic primary amino developing agent that has been made substantially nondiffusing in a hydrophilic colloid medium and in oxidized state forms a non-diffusing coupling product with a colour-forming reagent, which is itself not resistant to diffusion and which contains one or more reactive hydrogen atoms, such reagent on diffusion into the receptor material forming with its colour-forming reaction partner a dye by oxidative coupling.

Preferably used developing compounds are of the pphenylene diamine type and correspond to the following general formula:

4 5 l i 6 \12 N wherein:

each of R, and R represents an aliphatic residue including a substituted aliphatic residue in which optionally one of these residues is substituted with a polar group, e.g. an acidic group providing, e.g., substantivity to a hydrophilic colloid such as gelatin and/or facilitating the homogeneous distribution of said compounds in a hydrophilic colloid medium, preferred groups being a sulphonic acid, a carboxylic acid group or an alkylsulphonylamino group, or R represents the necessary methylene groups including substituted methylene groups to close a 5- or 6- membered heterocyclic nucleus with the carbon atom in the 6-position of the benzene nucleus, or R represents the necessary methylene groups including substituted groups to close a 5- or 6- membered heterocyclic nucleus with the carbon atom in the 2-position of the benzene nucleus, or R and R together represent the necessary methylene groups including substituted methylene groups to close a S-membered nitrogen containing nucleus, 7

R represents same or different substituents of the group comprising hydrogen or substitutents that have an influence on properties such as the developing capacity, binding force with the hydrophilic colloid or solubility in water, such as (an) alkyl group(s) e.g. (a) methyl group(s) or an alkoxy group such as methoxy or ethoxy, with the proviso that R in the cases that it does not represent hydrogen is limited to the 3- and/or 5- positions indicated above, and wherein said developing agent contains one or more substituents that provide the desired resistance to diffusion in a hydrophilic colloid medium e.g. at least one of said residues containing more than four carbon atoms in straight line.

The free amino group in the above p-phenylene diamine type compound may be mono-substituted with an alkyl group including a substituted alkyl group or an alkylene group ring-closed in the indicated 3- position. The free amino group may be blocked in a reversible way, e.g. by substitution with an alkyl group that is further substituted with an anionic group e.g. a sulphonic acid group, a carboxylic acid group, or a hypophosphorous acid group as described, e.g., in the United Kingdom Patent Specifications 691,815 filed Jan. 26, 1951 and 783,887 filed Aug. 30, 1954 both by Gevaert Photo-Producten N.V., and the Belgian Patent Specifications 535,687 and 535,688 both filed Feb. 14, 1955 and 557,556 filed May 16, 1957 all by Gevaert Photo- Producten N.V.

Other reversibly blocked p-phenylene diamine type developing agents in which the free amino group has reacted with an aldehyde so as to form a Schiffs base are described, e.g. in the US. Pat. No. 2,507,114 of David Malcolm, issued May 9, 1950, and the French Patent Specification 983,022 filed Oct. 20, 1948 by Kodak Pathe. Still other reversibly blocked pphenylene diamine type developing agents contain a phthalimide group as described in the US. Pat. Nos. 2,911,410 of David W. C. Ramsay, issued Nov. 3, 1959 and 2,930,693 of Karl Otto Ganguin and David William Crichton, issued Mar. 29, 1960.

Trialkyl p-phenylenediamines and their preparation are described in the Belgian Patent Specification 532,736 filed Oct. 22, 1954 by Gevaert Photo- Producten NV.

The preparation of other p-phenylene diamine type developers according to said general formula is known, e.g., from the United Kingdom Patent Specification 989,383 filed June 18, 1962 by Gevaert Photo- Producten NV. and 1,191,535 filed May 24, 1967 by Gevaert-Agfa NV. The introduction of a long aliphatic chain (containing at least four carbon atoms in straight line) can proceed according to techniques used in the production of non-diffusing colour couplers.

The preparation of preferably used non-diffusing pphenylene diamine type developing agents is described in the German Patent Applications P l93lO57.7 filed June 19, 1969 and P 203271 1.1 filed July 2, 1970 both by Agfa-Gevaert AG.

Preferably used non-diffusing p-phenylene diamine type developing agents correspond to the following general formula:

R represents hydrogen, an alkyl group, preferably a C C alkyl group e.g. methyl or ethyl, or an alkoxy group, preferably an alkoxy group containing at most three carbon atoms e.g. methoxy or ethoxy,

R represents hydrogen or an alkyl group, preferably a C C alkyl group e.g-. methyl or ethyl,

R represents a long chain aliphatic residue preferably a C,,C alkyl group, more preferably dodecyl, heptadecyl or octadecyl;

X represents hydrogen, a sulphonic acid group, a car- .boxylic acid group, a hydroxyl group, or a sulphonamido group in which the amido group may be substituted with short chain alkyl e.g. methyl or ethyl, and

n represents 1 to 4.

Particularly suited non-diffusing p-phenylene diaminetype developers are listed in the following table The non-diffusing p-phenylene diamine type developing agents also called herein primary developing agents are preferably used in combination with another reducing agent (i.e. an auxiliary developing agent) increasing the development speed. In respect thereof reference is made to pyrazolin-3-one developing compounds that may be added to the light-sensitive material and/or to the alkaline activating bath and correspond, e.g., to the following general formula:

wherein:

R represents an aryl group, including a substituted aryl group. e.g. phenyl,

R represents hydrogen or an acyl group such as acetyl and each of R R,, R and R (the same or different) represents hydrogen, an alkyl group, including a substituted alkyl group, or an aryl group including a substituted aryl group.

Good results are obtained with the following auxiliary developing compounds corresponding to the above formula III: 1-phenyl-pyrazolidin-3-one 1-(m-tolyl)- pyrazolidin-3-one 1-phenyl-2-acetyl-3-pyrazolidin- 3-one 1-phenyl-4-methy1-3-pyrazolidin-3-one 1- phenyl-S-methyl-3-pyrazolidin-3-one 1-phenyl-4,4- dimethyl-3-pyrazolidin-3-one 1-phenyl-5,5-dimethyl-3- pyrazolidin-3-one 1,5-diphenyl-3-pyrazolidin-3-one 1- (m-tolyl)-5-phenyl-3-pyrazolidin-3-one 1-(p-tolyl)-5- phenyl-3-pyrazo1idin-3-one Pyrazolidin-3-one developing compounds can be prepared according to preparation techniques described in the United Kingdom Patent Specifications 679,677, 679,678 both filed Apr. 6, 1950 and 703,669 filed Oct. 17, 1951 all three by llford Ltd. and in the US. Pat. No. 2,772,282 of Charles F. H. Allen and John B. Byers, issued Nov. 27, 1956.

Other reducing agents activating the developing action of the p-phenylene diamine type developing agent are developing compounds used in superadditive development such as described in the United Kingdom Patent Specifications '989,383 filed June 18, 1962 by Gevaert Photo-Producten N.V., 1,191,535 filed May 24, 1967 by Gevaert-Agfa N.V., 1,003,783 filed July 10, 1961 by Gevaert Photo-Producten NV. and 1,154,385 filed Nov. 4, 1966 by Agfa-Gevaert N.V.

More particularly good results are obtained with the following auxiliary developing agents:

rncc o-o l l m o o-er-r -HB1 no- CH:

(H5C2)2N \CHZ -HC1 CH2 1 (CI-ImCOOH (3H1 em N N U \/2HC1 ((EIIQy-SOQH A N I \CH:

When used in the activating bath the auxiliary developing agents are preferably applied therein in an amount of 50 mg to 2 g per litre.

ln saidfirst embodiment preferably a non-diffusing p-phenylene diamine type developing agent is used in combination with two reagents that are capable of diffusing in an alkaline hydrophilic colloid medium and that can oxidatively couple in alkaline medium by the action of a stronger oxidizing'agent than exposed silver halide to form a dye containing an azino group (=NN=).

One of said reagents called hereinafter compound A is capable of coupling with the non-diffusing oxidation product of the p-phenylene diamine type developing agent so that the coupling product is inhibited from diffusing into a receptor material.

Compound A can, e.g., be any compound suitable to act in a dye-forming electrophilic substitution reaction of which diazo coupling is an example. 1

Compound A is preferably'a compound of the type producing a quinone-imine or azomethine dye with an oxidizied N,N-dialkylp-phenylene diamine. Such compounds are sufficiently known to those skilled in the art of colour photography and are described, e.g., by Pierre Glafkides in Photographic Chemistry, Vol. ll Fountain Press London (1960), pages 596-604.

Suitable compounds A are, e.g. a-naphthol, phenol, reactive methylene type and reactive methyl couplers, i.e., diazo couplers as described, e.g., in the French Patent Specification l,602,473 filed Dec. 26, 1968 by Gevaert-Agfa N.V. Said compounds must have a chemical structure that allows them to diffuse by means of an alkaline aqueous liguid in a hydrophilic colloid medium e.g. gelatin.

In order to improve the diffusion mobility in an alkaline hydrophilic colloid medium it is desired that the coupler molecules contain a carboxylic acid or sulphonic acid group.

wherein:

each of R and R represents hydrogen, an alkyl group including a substituted alkyl group, an alkoxy group including a substituted alkoxy group, or the group NHR in which R represents a carboxylic acid acyl or sulphonic acid acyl group including said groups in substituted state, e.g. an aliphatic carboxylic acid acyl group, an aromatic carboxylic acid acyl group, an heterocyclic carboxylic acid acyl group e.g. a 2-fu'royl group or a 2-thienoyl group, an aliphatic sulphonic acid acyl group, an aromatic sulphonic acid acyl group, a sulphonyl thienyl group, an aryloxy-substituted aliphatic carboxylic acid acyl group, a phenylcarbamyl aliphatic carboxylic acid acyl group or a tolyl carboxylic acid acyl group, with the proviso that R and R not represent simultaneously hydrogen and the substituents are not of such type that the diffusion of the phenol compound in an alkaline hydrophilic colloid medium is markedly hindered; a polar substituent such as a carboxylic acid or a sulphonic acid group is preferably present as a substituent to improve the mobility of the phenol couplers in said medium.

The preparation of colour couplers that are within the scope of the above general formula is described, e.g., in the US Pat. No. 2,772,162 of Ilmari F. Salminen and Charles R. Barr, issued Nov. 27, 1956 and 3,222,176 ofJan Jaeken, issued Dec. 7, 1965 and in the United Kingdom Patent Specification 975,773 filed Sept. 4, 1961 by Gevaert Photo-Producten N.V.

Examples of suited phenol type couplers are listed in the following Table 2.

TABLE 2 C1 OH TABLE 2- Continued CH Oil Useful couplers are further a-naphthol type couplers 3 :gzrdisg s zlzltlmints; itsmsslzt H l) CON1-IR soar:

wherein V R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted 45 5 OH aryl group preferably such groups that are substil tuted with a carboxylic acid or sulphonic acid group.

These a-naphthol type couplers are prepared, e.g., by

a condensation reaction applying the phenyl ester of 50 g l-hydroicyfnaphthoic acid and the proper amine.

Examples of useful a-naphthol couplers are listed in the following Table 3. w

TABLE 3 Suitable reactive methylene type couplers correspond O NH S 03H to one of the following general formulae:

wherein:

R and R (same or different) each represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, a N- arylamino group including a substituted N- arylamino group, or an ether group including a substituted ether group, e.g. an alkoxy group,

R represents an alkyl group including a substituted alkyl group, or an aryl group including a substituted aryl group,

R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, carbethoxy, an alkoxy group, cyano, a N-arylamino group including a substituted N- arylamino group, a N-acylamino group including a substituted N-acylamino group or an ureido group including a substituted ureido group.

Methods for the preparation of said reactive methylene type couplers can be found,te.g., in the references given by P. Glafkides in his book Photographic Chemistry, Vol. 11 (1960) p. 597602 under the headings yellow couplers and magenta couplers and in the United Kingdom Patent Specifications 934,017 filed Jan. 25, 1962 by General Aniline & Film Corp, 1,062,203 filed July 6, 1964, 1,039,965 filed July 6, 1964, 1,007,847 filed Oct. 10, 1963, 1,066,334 filed Oct. 10, 1963 all four by Gevaert Photo-Producten NV. and 1,069,533 filed July 24, 1964 by Gevaert- Agfa N.V.

Preferred reactive methylene type couplers are listed in the following Table 4.

TABLE 4 COOII OCH:

OOOCHs OOCII:

In Order to illustrate the preparation of the open chain ketomethylene type couplers the preparation of the compounds 9, l and 11 of Table 4 is presented.

Compound 9 which becomes crystalline by stirring. The product is separated by filtration, washed with cyclohexane, and dried in a vacuum of 1 mm Hg at 50C.

Yield: 49 g or 90 percent.

Melting point: 155C.

Compound 10 A solution of 46.5 g (0.13 mole) of compound 9 of Tafie l iii a mixture of 465 ml of ethanol and ml of 5N aqueous sodium hydroxide is refluxed for 5 h whilst stirring. The precipitate formed being the product obtained by complete saponification is suctionfiltered and removed. A mixture of 500 ml of water and 50 ml of concentrated hydrochloric acid are added slowly to the filtrate whilst stirring, whereupon the precipitate formed is separated by filtration and dried.

The crude product is purified by crystallization from acetic acid and the crystals washed with chloroform. Purification is continued by recrystallization from nbutanol.

Yield: percent.

Melting point: 240C.

Compound 11 A solution of 46.5 g (0.13 mole) of compound 9 of Table 4 in a mixture of 465 ml of ethanol and 120 ml of 5N aqueous sodium hydroxide, is refluxed for 5 h whilst stirring and thereupon acidified with concentrated hydrochloric acid. The precipitate formed is suction-filtered and washed with methanol. The crude product is boiled three times in fresh n-butanol and finally washed with chloroform.

Yield: 79 percent.

Melting point: 260C.

Other suited couplers are:

N,N-dialkylanilines of the diffusing type containing as a further substituent on one of the alkyl groups, an acid substituent or a substituent containing an acid group, said acid group being present in free acid or salt form, e.g. a sulphonic acid substituent. The N,N-dialkylanilines couple with an oxidized N,N-dialkyl-p-phenylene diamine type developer to form a quino-diimine betaine type salt according to the following reaction scheme:

M is hydrogen, a metal cation or cationic group, e.g.,

an onium group, Y is a bivalent organic radical, e.g., an alkylene group, and R represents an alkyl group. Said dialkylanilines can be prepared according to known alkylating reactions for anilines.

Useful N,N-dialkylanilines of the diffusing type are listed in the following Table 5.

TABLE 5 lI3C-(CH2).

| s 0 H N-(CH N-C 0- T 2)2 S 0 H C2H Reagents called hereinafter compounds B, that by oxidative coupling with the above described compounds A form a dye containing an azino (=NN=) group are heterocyclic hydrazone compounds of the type that have diffusion mobility in an alkaline hydrophilic colloid medium. Useful heterocyclic hydrazone compounds are within the scope of the following general formula:

wherein:

R represents a CONH or SO X group in which X represents hydroxyl, an amino group including a substituted amino group, an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, and

Z represents the necessary atoms to close a 5 or 6- membered heterocyclic nucleus or ring system including such nucleus or ring system in substituted form.

Preferred heterocyclic hydrazone compounds correspond to the following formula:

f =L- 1 ':=N-1 m R7 R1 wherein:

R has the same meaning as described under formula R representshydrogen, an aliphatic group including a substituted aliphatic group, e.g an alkyl group including a substituted alkyl group, or an aromatic group including a substituted aromatic group, e.g. an aryl group including a substituted aryl group,

L represents a methine group or nitrogen,

n is 1 or 2, and

Z represents the necessary atoms to close a 5--or 6- membered heterocyclic nitrogen-containing nucleus or ring system including such nucleus or ring system in substituted form, e.g. a 2nucleus, nuclues, a 2-indolinylidene nucleus or a 4- quinolinylidene nucleus.

In view of an improved diffusion mobility in an alkaline hydrophilic colloid medium said hydrazone compounds contain preferably a carboxylic acid or sulphonic acid group.

Examples of useful hydrazone couplers are given in Table 6.

TABLE 6 (CH2)3 S 0311 TABLE 6 Continued 5.... (IJOOH moi-o COOII (Hzh-S 0 H CH; O O OH OOOH 0 COOH The preparation of said hydrazone compounds may proceed according to techniques described, e.g., in the United Kingdom Patent Specifications 975,932 filed Nov. 13, 1959, 990,628 filed Aug. 2, 1961 and 1,068,595 filed June 8, 1964 all three by Geugert Photo-ProductenNV. and the US. Pat. No. 3,293,032 of Jan Jaeken and Maurice Antoine de Ramaix, issued Dec. 20, 1966 and 3,525,614 of Jan Jaeken, Frans of dyes containing an azino group by oxidative coupling has been described, e.g., by S. Hunig, in Angew. Chem. 74, 818-821 (1962) and Ann. 609, 160 (1957), Ann. 617, l8l202 (1958), Ann. 623, 191-203 (1959), Ann. 636, 21-31 (1960), Ann. 640, 98-110 (1961), Ann. 641, 94-103 (1961), Ann. 647, 6676 (1961), Ann. 651. 89-101 (1962).

Developing agents that in oxidized state can couple with said hydrazone compounds and prevent these compounds from diffusing out of a hydrophilic colloid layer to a receptor material are aromatic 1,2-dihydroxy compounds that on coupling with the hydrazones form sufficiently large molecules that are immobilized in the hydrophilic colloid in which they are formed. Examples of such useful 1,2-dihydroxy compounds are listed in the following Table 7.

TABLE 7 In order to produce a coupler molecule having a sufficiently poor diffusion mobility in a hydrophilic colloid medium residues are introduced, which improve the resistance to diffusion. Suited for that purpose are organic residues that are photographically inert or at least do not give rise to fog in a silver halide emulsion layer and that consist of or comprise a straight or branched chain aliphatic group of preferably at least 8 carbon atoms. Such residues may be linked to the compound, which has to be made resistant to diffusion, either directly by a carbon-carbon link or by the intermediate of groups such as CONH, SO NH, CO, SO O, Sor NR- wherein R represents hydrogen or alkyl. The presence of a residue, which makes the molecule of the developing agent resistant to diffusion, does not exclude, however, the presence of one or more polar groups, which improve the compatibility with the hydrophilic colloid and facilitates the homogeneous distribution of the developing agent in the hydrophilic colloid. Suitable polar groups for that purpose are, e.g., carboxyl groups and sulphonic acid groups in free acid or salt form.

In the cases in which the molecule that has to be resistant to diffusion is large enough, e.g., for it comprises more than one aromatic or heterocyclic nucleus and no polar groups, the introduction of long chain aliphatic residues is not necessary at all or lower alkyl groups (C -C may suffice.

Apart from the hydrazones that by oxidative coupling yield azino dyes with, e.g., a-naphthol, phenol, or reactive methylene type couplers, other oxidatively dyeforming compounds can be applied that are known, e.g., from photographic integral masking techniques according to which a dye image is formed by oxidative coupling in a potassium cyanoferrate(lll) bleaching bath. For such colourless compounds known from integral masking reference is made, e.g., to 4- aminopyrazolones corresponding to the following general formula:

(XII) wherein:

each of R and R represents an alkyl group of at most five carbon atoms, and

R represents an alkyl group of at most five carbon atoms, a phenyl group including a substituted phenyl group.

The preparation of said 4-aminopyrazolones and their use in oxidative coupling for masking purposes has been described in the United Kingdom Patent Specifications 880,862 filed Dec. 31, 1956 by Gevaert Photo-Producten N.V. and the US. Pat. No. 3,012,884 of Maurice Antoine de Ramaix and Jan .laeken, issued Dec. 12, 1961 and 3,013,879 of Maurice Antoine de Ramaix and Jan Jaeken, issued Dec. 19, 1961.

Other suitable oxidatively coupling dye-forming compounds are p-phenylene diamines with sterically hindered amino group and sterically hindered phenols as described, e.g., in the United Kingdom Patent Specification 1,153,561 filed Jan. 18, 1966 by Agfa-Gevaert N.V. and 975,940 filed Nov. 30, 1959 by Gevaert Photo-Producten N.V. respectively.

A multilayer photographic material suited for use according to the first embodiment of the present invention in the formation of multicolour images by imagewise diffusion transfer of dye-forming reactants from a photographic material into a receptor material comprises:

1. a blue-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents that are capable of diffusing in said medium when wetted with an aqueous alkaline liquid and of forming a yellow dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,

2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents, that are capable of diffusing in said medium when wetted with an aqueous alkaline liquid and of forming a magenta dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,

. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents that are capable of diffusing in said medium when wetted with an alkaline aqueous liquid and of forming a cyan dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than such reagent has in unreacted state; and any said reagent, which does not form a compound photographic material one of the reaction partners of each pair of partners has to be common to all of the pairs and those partners that are not common are to be immobilized by reaction with one or more oxidation products of a developing agent or agents. The partner that is common to all of the pairs may be applied in hydrophilic colloid layers that are adjacent to the silver halide emulsion layers. Each silver halide emulsion layer may be separated from an other silver halide emulsion layer by a suitable spacer stratum, e.g., by a layer of gelatin or polyvinyl alcohol. The spacer stratum may act as a kind of a permeable barrier layer controlling the diffusion of the dye-forming compound(s), e.g., is a layer of slowly permeable material, such as a layer of cellulose acetate-hydrogen phthalate occasionally in combination with a more water-permeable spacer layer, e.g., gelatin layer.

In the already mentioned second embodiment of the present invention for multicolour reproduction by subtractive colour photography producing yellow, magenta and cyan dyes, three different compounds C,C are used in which one group either C or C has the same structure in these three compounds or is of the same chemical type, i.e., operates along the same chemical reaction mechanism (e.g. electrophilic or nucleophilic substitution) preferably with substantially the same reaction speed.

Useful sets of colour-forming reagents C -C for three colour materials with true colour reproduction possibilities in multicolour photography contain a same structural colour-forming part and may be represented, e.g., by the following sets of chemically linked reactive molecule parts A, B, C, X, Y and Z:

Preferably the C,C compounds that are suitable for intermolecular or intramolecular coupling have a C, chemical structural part capable of forming a quinonimine or azomethine dyestuff structure with an ozidized p-phenylene-diamine type developing agent, and a C chemical structural part containing a hydrazone group, which enables the C -C compound under oxidative conditions to form a dye containing an azino (=NN=) group.

In particularly suited C,-C compounds the part C, is a group containing the structure of an a-naphthol coupler and corresponds to the formula:

or is a group containing the structure of a reactive methylene type coupler and corresponds to one of the following general formulae: XIII.

-l-INCOCI-I -COR HNCOCH CN (XIV) l i HiooR" wherein:

R represents an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group, an alkoxy group or a substituted amino group, e.g. an alkyl or aryl substituted amino group, and

R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, cyano, an alkoxy group, a carbonylalkoxy group, a N-arylamino group including a substituted N-arylamino group, a N-acylamino group in- 1 in which Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nucleus or ring system including such nucleus or ring system in substituted form.

Particularly suitable C,C compounds contain a group C corresponding to the following general formula:

(XVI) R2 wherein:

R represents hydrogen, an aliphatic group including a substituted aliphatic group or an aromatic group including a substituted aromatic group,

L represents methine or nitrogen, n is 1 or 2, and

2, represents the necessary atoms to close a 5- or 6- membered heterocyclic nucleus or ring system, said nucleus or ring system being either or not in substituted form.

Compounds that produce a dyestuff by oxidative intramolecular coupling (except for compound 18 that couples intermolecularly) and that contain a common naphthol methylene coupler part C, and a hydrazone part C are illustrated by the following examples in Table 8. below.

Compound HOsS-@ given hereinafter for illustrative purposes.

Compound 1 is prepared from compound 6 by saponification of the fluorosulphonyl group with sodium hydroxide.

Preparation of compound 14 Reactlon sc heme A Preparation of Compound 6 Reaction scheme (III) mN Nml-ito compoundG The intermediate compound (III)(melting point:

210C) has been prepared by a technique known for preparing a-hydroxy-B-naphthoic acid anilides starting from p-fluorosulphonylaniline and the phenyl ester of a-hydroxy-B-naphthoic acid.

Said intermediate compound (III) was allowed to react with hydrazine hydrate dissolved in dioxan so as to form a sulphonylhydrazine (IV) (melting point: 245C).

This sulphonylhydrazinde (IV) was used in the preparation of the compounds 1 to 6 and 8 to 13.

More particularly, in the preparation of compound 6 the sulphonylhydrazine (IV) was applied in a condensation reaction with l-methyl- 2-phenyl-6- fluorosulphonyl-4-chloro-quinolinium methyl sulphate, the preparation of which is described in the Belgian Patent Specification 745,438 filed Feb. 4, 1970 by Gevaert-Agfa N.V.

Ha tam-Nam; Fozs Q-NHCOCH;

l Cl 0113 4 (I) (II) (III) 30.4 g of sulphonylhydrazide (II) are dissolved in 300 ml of a mixture of chloroform and dry ethanol (1:1 by volume) and allowed to react with 59 g of the quinolinium compound (I) with stirring and refluxing for 2 h. Thereupon the solvents are distilled and to the residue 300 ml of a solution of hydrochloric acid (10 percent) in ethanol are added. Refluxing is started again and maintained for 4 h. Upon cooling the obtained hydrochloride is separated and washed with acetone. The hydrochloride is dissolved in a minimum amount of pyridine and poured into a ten-fold amount of water;

First the obtained product (III) is thoroughly washed with water and then with methanol.

Yield: 52.6 g.

Melting point: about 240C.

Reaction Scheme B 111) -oocmooootm Reaction scheme C NaOH acetone/ H 20 20 g of the sulphofluoride (V), 33 ml of sodium hydroxide (30 percent by weight in water) and 200 ml of acetone are refluxed for 30 min. with stirring.

(V)+ compound 14 Preparation of compound 16 Reaction scheme al Y N N rwnn-smQ-rrm Q I l (III) To a solution of 9.7 g (0.02 mole) of amino compound (l) in 48.5 ml of acetic acid a solution of 4.9 g

(0.03 mole) of the pyrazole compound (II) in 48.5 ml.

of acetic acid is added. The reaction mixture is stirred for 5 h at C whereupon it is pouredin'to l l of water, salted out and stirred for min. The obtained hydrochloride (III) is separated by suction, washed with methanol and dried.

Melting point: 210C (decomposition).

Yield:' 12 g.

Preparation of Compound 17 -Qjl ( JOCHMJN COCHzCN The reaction mixture is then acidified with 2N hydrochloric acid and poured into 500 ml of water. The precipitate is suction-filtered and washed with water till neutral. A further thorough wash with acetonitrile and methanol yields 7 g of compound (III).

Melting point: 260C.

A particular advantage of the intramolecularly reactive compounds C C resided in the fact that the reactive parts C and C reach the receiving material in perfect stoechiometric amounts so that practically no undesired colour fog is produced in the diffusion transfer picture and very clear whites are obtained.

Because two oxidatively colour-forming parts are united in one molecule, only one molecule of oxidized developing agent is necessary to immobilize the united parts, whereas when these parts represent separate compounds each of them is to be immobilized at the expense of two molecules of oxidized developing agent and a corresponding larger amount of silver halide.

Further, since in this second embodiment only three colour-formingreagents have to be transferred by dif- DMF (III) 11 g (0.0227 mole) of amino compound (I) are dissolved in a mixture of 70 ml of dimethyl-formamide and 5.5 ml of triisopropanolamine. To the obtained solution 7.35 g of the pyrazole compound (ll) dissolved in 40 ml of dimethylformamide are added. The mixture is stirred for 4 h at room temperature and thereupon an additional amount of 3.67 g of the pyrazole compound is introduced. Thereafter stirring is continued for another 2 h.

fusion, it is much easier to bring the composition in colour balance than in a process wherein at least four reagents are applied as is the case according to the first embodiment for multicolour reproduction.

According to the second embodiment of the present invention useful for the formation of a dye image of an individual colour on a receptor material, a photosensitive recording material is used comprising a sheetlike support and a hydrophilic colloid silver halide emulsion layer containing in effective contact with the silver halide a non-diffusing p-phenylenediamino type developing agent and said compound C -C which is capable to diffuse out of the hydrophilic colloid layer by means of an alkaline aqueous liquid.

Compound C C is incorporated into the same silver halide emulsion layer or into a colloid layer subjacent to the silver halide emulsion layer so that the compound that has to be immobilized can be intercepted by the oxidized non-diffusing developing agent.

The silver halide emulsion layer composition may contain spectral sensitizing agents.

Useful spectral sensitizing agents are in the class of the methine dyes, e.g., the cyanine dyes, hemicyanine, merocyanine, oxonol, hemi-oxonol and styryl dyes and polynucleic methine dyes such as rhodacyanine dyes and neocyanine dyes. Such sensitizing agents are described by F. M. Hamer in his book The Cyanine Dyes and Related Compounds (1964).

Preferably used cyanine dyes have a betaine-like structure owing to the presence on the nitrogen atom of at least one'of the heterocyclic nuclei of an alkyl group wherein each of R and R is hydrogen or a hydrocarbon radical, at least one of them being hydrogen.

Suitable spectral sensitizing dyes of that type are described, e.g. in the United Kingdom Patent Application 16,998/70 filed Apr. 9, 1970 by Agfa-Gevaert NV. and in the published Dutch Patent Application 7004174 filed Mar. 24, 1970 by Agfa-Gevaert N.V.

Preferably used merocyanine dyes are the so-called zeromethine and dimethine merocyanine dyes containing a barbituric acid or thiobarbituric acid nucleus, e.g. as described in the US. Pat. No. 2,170,807 of Leslie 6. S. Brooker, issued Aug. 20, 1939 and the German Democratic Republic Patent Specification 12,477 filed Sept. 20, 1954 by G. Back and J. Brunken.

The silver halide emulsion layer(s) may further contain the usual additives such as e.g., antifogging agents, chemical sensitizing agents, stabilizing agents, development accelerators, plasticizers, hardening agents and wetting agents.

The photosensitive material may contain any type of support known for silver halide photographic materials but comprises preferably a flexible support, e.g., a

paper or plastic film base in sheet, web or ribbon form. For reflex exposure purposes a photographic material with a transparent or semi-transparent (at least 50 percent light transmission) support is used.

According to a preferred embodiment the imagereceiving material is a flexible plastic film or a paper sheet coated with a hydrophilic colloid layer containing an oxidizing agent that is capable of effecting the oxidative coupling of the couplers as defined above and which has a structure that makes it difficult or impossible to leave said hydrophilic colloid layer by diffusion in an aqueous alkaline liquid.

Examples of suitable oxidizing compounds are nondiffusing organic peroxides, long chain (C -C20) aliphatic onium salts of peracids and compounds that easily split off halogen in aqueous medium such as halogen amides and imides, examples of which are bromosuccinimide and non-diffusing chloramine T and dichloramine T type compounds.

Examples of such compounds are listed in Table 9.

TABLE 9 (2) CIHQ.

Hfi-I nn 15-0113 slot- CH3 2 O=C C=O (l: H: CH3

Useful receiving materials contain in a hydrophilic colloid layer, e.g., incorporated in gelatin an amount of 0.01-0.05 mole of dibenzoyl peroxide per sq.m.

The image-receiving element may contain agents adapted to mordant or otherwise fix the dyes, e.g. azine dyes, formed by oxidative coupling. For example the image-receiving element contains a polymer, preferably a cationic polymer that acts as a mordant for anionic dyes as described e.g. in the United Kingdom Patent Specification 1,221,195 filed Mar. 26, 1968 by Gevaert-Agfa NV. The mordanting agent may be applied in admixture with the oxidizing agent or in a layer adjacent to the layer containing the oxidizing agent.

The aqueous alkaline activating liquid has preferably a pH between 8 and 13 and contains, e.g., from to 50 g of sodium carbonate-per litre. It may contain development accelerating compounds, viscositycontrolling agents, e.g. hydroxyethylcellulose, wetting agents and water-miscible organic liquids for the purpose of improving the density of the dye image on the receptor material.

The activating liquid may be applied to the photosensitive material after its exposure by any technique known in the art of applying liquids to sheet materials, e.g., by spreading, imbibition, liquid film coating practices or spraying and may be similarly applied to the image-receiving element before the latter and the photosensitive material are brought into superposed relation or contact for carrying out the diffusion transfer of oxidatively coupling compounds from the undeveloped portions.

The alkaline agent may also be applied in pods or pressure-rupturable micro-containers, e.g., microcapsules, and squeezed into contact with the receptor material.

In the preparation according to the first embodiment of the present invention of a multicolour image by selective image-wise modulated diffusion transfer of the proper pairs-of oxidatively dye-forming compounds A and B, preferably multilayer photosensitive materials are used as illustrated in the accompanying FIGS. 1 and 2.

A multilayer photosensitive element according to FIG. 1 comprises a blue-sensitive silver halide emulsion layer 1 containing a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A that in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with an alkalisoluble reagent B and forms a yellow dye after diffusion onto a receptor material containing the stronger oxidant.

Element 2 is a hydrophilic colloid spacer layer, eg a gelatin layer.

Element 3 is a green-sensitive silver halide emulsion layer that is substantially insensitive to blue and red light and contains a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A ma in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with a same alkali-soluble reagent B and forms a magenta dye after diffusion onto the receptor material containing the stronger oxidant.

Element 4 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.

Element 5 is a red-sensitive silver halide emulsion layer that is substantially insensitive to blueand green light and contains a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A that in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with a same alkali-soluble reagent B and forms a cyan dye after diffusion onto the receptor material containing the stronger oxidant.

LII

Element 6 is a subbing layer for a gelatino silver halide colloid layer and a support 7, which is, e.g., a film support or semi-transparent paper base.

A multilayer photosensitive element according to FIG. 2 contains a blue-sensitive silver halide emulsion layer 1 containing a non-diffusing silver halide developing agent and an alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a yellow dye with an alkalisoluble coupler A, that is present in the hydrophilic water-permeable colloid layer 2.

The coupler A, diffusing out of the colloid layer 2 and penetrating into the exposed emulsion layer 1 reacts therein with the non-diffusing developer oxidation products and is inhibited thereby from further migration.

Element 3 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.

Element 4 is a green-sensitive silver halide emulsion layer that is substantially insensitive to blue and red light and contains a non-diffusing silver halide developing agent and a same alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a magenta dye with an alkali-soluble coupler A that is present in a hydrophilic water-permeable colloid layer 5.

Element 6 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.

Element 7 is a red-sensitive silver halide emulsion layer that is substantially insensitive to blue and green light and contains a non-diffusing silver halide developing agent and a same alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a cyan dye with an alkali-soluble coupler A that is present in a hydrophilic water-permeable colloid layer 8.

Element 9 is a subbing layer, e.g., a gelatin layer and element 10 is a support, e.g., a paper support.

In the composition of the photographic recording materials as illustrated in FIG. 1 and FIG. 2 the following reaction partners A and B capable of diffusing in alkaline medium through a hydrophilic colloid mass are mentioned as examples of practice.

A's common mobile reaction partner B a hydrazone compound having the following structural formula may be used:

nd Q-ooomoormQooon 'fifil'loivf'hiine dye formed with compouF(A )fi and the hydrazone B has the following structure:

(IZFa (1H2 N s l fi 5 H160 \FNN=CCNH2 (CHDs-SOgNfl 7 As mobile reaction partners A capable of forming a magenta azine dye with said common partner B the following reactive alkali-soluble aromatic hydroxy couplers(A' and (A" may be used.

CONH(CH2)2SO3H z) and NHCO \0/ E000 (CH2)2CONH The magenta azine dye formed with compound (A' and the hydrazone B has the following structure:

C0NH(CHz)zSO H (CHDr-SOzNa As mobile reaction partners A capable of forming a cyan azine dye with said common partner B the following reactive alkali-soluble sulpho-substituted N,N- dialkylanilines (A;,) and (A";,) may be used:

Habits N 7 it s s Holscm). 5

CzH5

The cyan azinc dye formed with compound (A' and 5 the hydrazone B has the following structure: 5

CHa-CH3 moo TN-IL (GEN-:" l

(CH2)aSOaNa In order to improve the reactivity to couple with the oxidation products of a non-diffusing p-phenylenediamine type developing agent a reactive CH group may be introduced in one of the alkyl groups,

e.g. as exemplified in the following N,N-dialkylanilino coupler:

The introduced reactive methylene group does not influence the absorption of the finally formed azine dye in the visible spectrum since the chromophoric system formed with the aid of that methylene group will only cause absorption in the non-visible short wave ultraviolet range.

A p-phenylenediamine type developing agent that is resistant to diffusion in an alkaline hydrophilic colloid medium and is particularly useful for application according to the present invention has the following formula:

S 03H t 2) n SOQH A multilayer photographic material suited for use according to the second embodiment of the present invention in the formation of multicolour images by imagewise diffusion transfer of intramolecularly or intermolecularly dye-forming reactants from a photographic material into a receptor material comprises preferably:

1. a blue-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colourless reagent A-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a yellow dyestuff by oxidative intramolecular or intermolecular coupling, and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state,

2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colourless reagent A-Y or B-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a magenta dyestuff by oxidative intramolecular or intermolecular coupling and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state,

3. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a colourless reagent A-Z or C-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a cyan dyestuff by oxidative intramolecular or intermolecular coupling and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state.

Each silver halide emulsion layer may be separated from another silver halide emulsion layer by a suitable 

1. DIFFUSING IN AQUEOUS ALKALINE MEDIUM FROM SAID MATERIAL TO A RECEPTOR MATERIAL,
 1. A PROCESS FOR THE FORMATION OF TRANSFER IMAGES INCOLOR COMPRISIING THE STEPS OF: A. IMAGEWISE EXPOSING TO ELECTROMAGNETIC RADIATION A PHOTOGRAPHIC MATERIAL, WHICH CONTAINS A SILVER HALIDE EMULSION LAYER INCLUDING THE SILVER HALIDE GRAINS WHICH ARE SENSITIVE TO SAID ELECTROMAGNETIC RADIATION AND IN EFFECTIVE CONTACT WITH SAID GRAINS A DEVELOPING AGENT THAT IS RESISTANT TO DIFFUSION IN A HYDROPHILIC COLLOID MEDIUM, SAID LAYER ALSO CONTAINING IN EFFECTIVE CONTACT WITH SAID DEVELOPING AGENT A COLORLESS REAGENT CAPABLE OF:
 2. A process according to claim 1 wherein the silver halide emulsion layer contains a non-diffusing silver halide developing agent the oxidation product of which forms a reaction product with a phenol-type or reactive methylene type coupler.
 2. FORMING A DYESTUFF BY OXIDATIVE COUPLING, AND
 2. forming a dyestuff by oxidative coupling, and
 2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colorless compound of said formula C1-C2 that is capable of diffusing in said medium with an alkaline aqueous liquid, of forming a magenta dyestuff by oxidative intramolecular or intermolecular coupling, and of forming with the oxidation product of said developing agent a compound of substantially reduced diffusion mobility, and
 2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a colorless coupler and hydrazone compound that are capable of diffusing in said medium when wetted with an alkaline aqueous liquid and of forming a magenta dyestuff by oxidative coupling with each other and wherein at least one of said coupler and compound is capable of forming with the oxidation product of the developing agent a compound of substantially lower diffusion mobility than the unreacted compound, and
 2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colorless dye-forming reagent of said formula C1-C2 that is capable of diffusing in said medium with an alkaline aqueous liquid, of forming a magenta dyestuff by oxidative intermolecular or intramolecular coupling, and of forming with the oxidation product of said developing agent a compound of substantially reduced diffusion mobility, and
 2. a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent in effective contact therewith a non-diffusion resistant colorless coupler that is capable of forming with the developer oxidation product a compound of substantially reduced diffusion mobility and capable of forming a magenta dyestuff by oxidative coupling with the same hydrazone compound as used in the blue-sensitive silver halide emulsion layer, and
 3. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a non-diffusion resistant colorless coupler that is capable of forming with the developer oxidation product a compound of substantially reduced diffusion mobility and capable of forming a cyan dyestuff by oxidative coupling with the same hydrazone compound as used in the blue-sensitive silver halide emulsion layer.
 3. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a colorless dye-forming reagent of said formula C1-C2 that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a cyan dyestuff by oxidative intermolecular or intramolecular coupling, and of forming with the oxidation product of said developing agent a compound of substantially reduced diffusion mobility.
 3. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a colorless coupler and hydrazone compound that are capable of diffusing in said medium when wetted with an aqueous alkaline liquid and of forming a cyan dyestuff by oxidative coupling with each other and wherein at least one of said coupler and compound is capable of forming with the oxidation products of the developing agent a compound of substantially lower diffusion mobility than the unreacted compound; wherein said hydrazone compound of each such layer is the same and corresponds to the general formula of the first hydrazone compound of claim 28, b. contacting the exposed photographic material with an aqueous alkaline processing liquid, which starts the reducing action of such developing agent thereby forming in correspondence with the latent silver image portions of each silver halide emulsion layer a visible silver image and a developer oxidation product, which couples in its silver halide emulsion layer with at least one of said coupler and hydrazone compound to form a Compound of substantially reduced diffusion mobility, c. transferring from the treated material from step (b) residual unaffected dye-forming coupler and compound by means of the alkaline processing liquid into a receptor material wherein the coupler and hydrazone compound of each layer are oxidatively coupled together by means of an oxidant stronger than exposed silver halide resulting in the formation in the receptor material of a positive multicolor print of the multicolor light pattern.
 3. a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colorless compound of said formula C1-C2 that is capable of diffusing in said medium with an alkaline aqueous liquid, of forming a cyan dyestuff by oxidative intramolecular or intermolecular coupling, and of forming with the oxidation product of said developing agent a compound of substantially reduced diffusion mobility, b. contacting the exposed photographic material with an aqueous alkaline liquid, which starts the reducing action of such developing agent thereby forming in correspondence with the latent silver image portions of each silver halide emulsion layer a visible silver image and a developer oxidation product, which couples in its silver halide emulsion layer with the corresponding colorless compound to form a compound of substantially reduced diffusion mobility, c. transferring from the treated material the different residual unaffected colorless compounds with the alkaline processing liquid into a receptor material wherein the different compounds are intramolecularly or intermolecularly oxidatively coupled by means of an oxidizing agent which is stronger than exposed silver halide, resulting in the formation in the receptor material of a positive multicolor print of the multicolor light pattern.
 3. FROMING WITH THE OXIDATION PRODUCT OF SAID DEVELOPING AGENT A COMPOUND OF SUBSTANTIALLY REDUCED DIFFUSION MOLBILITY, B. CONTACTING THE EXPOSED PHOTOGRPHIC MATERIAL WITH AN AQUEOUS ALKALINE ACTIVATING LIQUID TO BRING ABOUT THE REDUCING ACTION OF THE DEVELOPING AGENT THEREBY FORMING IN THE EXPOSED PORTIONS A SILVER IMAGE AND AN OXIDATION PRODUCT OF THE DEVELOPING AGENT THAT REACTS WITH SUCH COLORLESS REAGENT TO FORM IN THE EXPOSED PORTIONS OF THE EMULSION LAYER SAID COMPOUND OF SUBSTANTIALLY REDUCED DIFFUSION MOBILITY AND C. TRANSFERRNG FROM THE TREATED MATERIAL AN AMOUNT OF SUCH COLORLESS REAGENT ONTO A RECEIVING MATERIAL WHEREON SUCH TRANSFERRED REAGENT IS SUBJECTED TO OXIDATIVE COUPLING BY MEANS OF AN OXIDIZING AGENT STRONGER THAN EXPOSED SILVER HALIDE RESULTING IN THE FORMATION OF AN IMAGE OF SAID DYESTUFF ON THE RECEIVING MATERIAL, SAID COLORLESS REAGENT BEING (A) THE COMBINATION OF A COLORLESS COUPLER CAPABLE OF FORMING A QUINONIMINE OR AZOMETHINE DYESTUFF WITH AN OXIDIZED P-PHENYLENE DIAMINE DEVELOPING AGENT AND A HETEROCYLIC HYDRAZONE COMPOUND CORRESPONDING TO THE FOLLOWING GENERAL FORMULA:
 3. forming with the oxidation product of said developing agent a compound of substantially reduced diffusion mobility, b. contacting the exposed photographic material with an aqueous alkaline activating liquid to bring about the reducing action of the developing agent thereby forming in the exposed portions a silver image and an oxidation product of the developing agent that reacts with such colorless reagent to form in the exposed portions of the emulsion layer said compound of substantially reduced diffusion mobility and c. transferring from the treated material an amount of such colorless reagent onto a receiving material whereon such transferred reagent is subjected to oxidative coupling by means of an oxidizing agent stronger than exposed silver halide resulting in the formation of an image of said dyestuff on the receiving material, said colorless reagent being (A) the combination of a colorless coupler capable of forming a quinonimine or azomethine dyestuff with an oxidized p-phenylene diamine developing agent and a heterocyclic hydrazone compound corresponding to the following general formula:
 3. A process according to claim 1 wherein the contacting of the exposed photographic material with an alkaline aqueous liquid occurs in the presence of a primary developing agent that is resistant to diffusion and of an auxiliary developing agent.
 4. A process according to claim 1 wherein the receiving material contains in a water-permeable image-receiving layer at least one oxidizing agent of the group comprising a non-diffusing organic peroxide, a long chain aliphatic onium salt of a peracid and a compound that splits off halogen in aqueous medium.
 5. A process according to claim 4 wherein the receiving material contains as a mordanting agent for the dye formed thereon a polymer containing cationic groups.
 6. A process according to claim 1 wherein the alkaline aqueous processing liquid contains at least one alkaline compound of the group comprising alkali metal carbonates, alkali metal hydroxides and aliphatic amines.
 7. A process according to claim 1 for the formation of multicolor images with a photographic material containing three superposed silver halide emulsion layers, which are sensitive to blue, green and red light respectively, said process comprising the steps of: a. exposing to a multicolor light pattern a photographic material which comprises:
 8. A process according to claim 1 for the formation of multicolor images by imagewise transfer of a composite compound of the formula C1-C2 as in claim 28 from a photographic material containing three superposed silver halide emulsion layers that are sensitive to blue, green and red light respectively, said process comprising the steps of: a. exposing to a multicolor light pattern a photographic material which comprises:
 9. A photographic process according to claim 1 wherein said developing agent is a compound the oxidation product of which forms a diffusion inhibited reaction product with an Alpha -naphthol, phenol, reactive methylene type coupler of a N,N-dialkylaniline type coupler.
 10. A photographic process according to claim 9 wherein said developing agent is an aromatic primary amino developing agent.
 11. A photographic process according to claim 10 wherein the developing agent corresponds to the following general formula:
 12. A photographic process according to claim 1 wherein said coupler which is capable of forming with the developer oxidation product a compound of substantially reduced diffusion mobility is a phenol, Alpha -naphthol, a reactive methylene type of an N,N-dialkyl-aniline type coupler.
 13. A photographic material suitable for the production of dye images by imagewise diffusion transfer of compounds soluble in an aqueous alkaline processing liquid, which material contains a. photosensitive silver halide grains dispersed in a hydrophilic colloid layer and b. in such layer or in water-permeable relationship to such layer a colorless reagent capable of forming a dyestuff by an oxidative coupling reaction and of diffusing in an aqueous alkaline medium from said material to a receptor material, and c. in effective contact with said silver halide grains a developing agent which is resistant to diffusion in a hydrophilic colloid medium and which when activated in the presence of an aqueous alkaline liquid after the imagewise exposure of said layer reduces the exposed silver halide in said layer and couples in its oxidized state with said colorless reagent to form a product inhibited against diffusion from the exposed portions of the photosensitive material into the receptor material, and wherein said colorless reagent in said photographic material is A. the combination of a colorless color coupler capable of forming a quinonimine or azomethine dyestuff with an oxidized p-phenylene diamine developing agent and a heterocyclic hydrazone compound of the following general formula:
 14. A photographic material according to claim 13 wherein the colorless color coupler is a phenol, Alpha -naphthol, or reactive methylene type of a N,N-dialkylaniline type coupler.
 15. A photographic material according to claim 14 wherein said colorless coupler is a phenol having the general formula:
 16. A photographic material according to claim 14 wherein said colorless coupler is an Alpha -naphthol having the general formula:
 17. A photographic material according to claim 14 wherein said colorless coupler corresponds to one of the following general formulae: R1-CO-CH2-CO-R2 (I) R1-CO-CH2-CN (II) and
 18. A photographic material according to claim 14 wherein said colorless coupler is a N,N-dialkylaniline having the general formula:
 19. A photographic material according to claim 13 wherein said developing agent has the general formula:
 20. A photographic material according to claim 13 wherein said moiety C1 is a group derived from an Alpha -naphthol coupler which corresponds to the formula:
 21. A photographic material according to claim 13 wherein said moiety C1 is a group derived from a non-diffusion resistant reactive methylene type coupler corresponding to one of the following general formulae: -HN-CO-CH2-CO-R2(I) and -HN-CO-CH2-CN(II)
 22. A photographic material according to claim 13 wherein the silver halide grains are present in a hydrophilic colloid layer on a flexible support.
 23. A photographic material according to claim 22 wherein the support is a paper or plastic film support.
 24. A photographic material according to claim 13 adapted for use in the formation of multicolor images by imagewise diffusion transfer of dye-forming reactants from a photographic material onto a receptor material, which photographic material comprises:
 25. A photographic material according to claim 13 adapted for use in the formation of multicolor images by imagewise diffusion transfer of dye-forming reactants from a photographic material onto a receptor material, which photographic material comprises: 